GB2108115A - Polycarbamates and use as surfactants - Google Patents

Polycarbamates and use as surfactants Download PDF

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Publication number
GB2108115A
GB2108115A GB08226259A GB8226259A GB2108115A GB 2108115 A GB2108115 A GB 2108115A GB 08226259 A GB08226259 A GB 08226259A GB 8226259 A GB8226259 A GB 8226259A GB 2108115 A GB2108115 A GB 2108115A
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mol
occurrence
theory
same
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GB08226259A
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Dr Lorenz Heiss
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
    • D06P1/6073—Nitrogen-containing polyethers or their quaternary derivatives containing CON=, OCON=, SO2N=, OSO2N= groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/655—Compounds containing ammonium groups
    • D06P1/66—Compounds containing ammonium groups containing quaternary ammonium groups

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

A cross-linked polycarbamate of the formula <IMAGE> in which each R1 independently represents an optionally substituted (C1-C30)-alkyl or (C1-C30)-alkenyl radical, and each R2 independently represents a benzyl radical, or an optionally substituted (C1-C30)-alkyl or (C1-C30)-alkenyl radical, with the proviso that the sum of the carbon atoms present in R1 and R2 must be at least 10, A and B each independently represents a group of the formula -C2H4O- or -C3H7O-, x and y each is zero to 30, with the proviso that the sum of x and y is at least 1, each m is 1 to 60, z is 1 to 6, R3 represents a hydrogen atom or an alkali metal or alkaline earth metal cation, and An<(-)> is a halide, alkylsulphate or alkylphosphate ion, his use as a surfactant.

Description

SPECIFICATION Polywarbamates, process for their preparation, and method for their use The invention relates to polycarbamates, process for their preparation and method for their use.
The present invention provides a cross-linked polycarbamate of the general formula
in which R1, which may be the same or different at each occurrence, represents a (C1-C30)-alkyl or (C1- C30)-alkenyl radical, each of which may be unsubstituted or substituted by one or more substituents, and R2, which may be the same or different at each occurrence, represents a benzyl radical, or a (C1- C30)-alkyl radical, preferably methyl, each of which may be unsubstituted or substituted by one or more substituents, with the proviso that the sum of the carbon atoms present in R and R2 must be at least 10, A and B, which may be the same or different at each occurrence, each represents a group of the formula -C2H4O- or -C3H7O-, x and y, which may be the same or different at each occurrence, each number in the range of from zero to 30, with the proviso that the sum of x and y is at least 1, m is a number in the range of from 1 to 60, and may be the same or different at each occurrence, z is a number in the range of from 1 to 6, R3 represents a hydrogen atom or an alkali metal or alkaline earth metal cation, and Ane represents a chloride, bromide, methosulphate or methophosphate ion.
The alkyl or alkenyl groups, represented by R1 may be straight chain/branched chain radicals and may be substituted by one or more substituents selected from chlorine, bromine, nitro, hydroxy and lower alkoxy groups. Preferably, however, the alkyl groups R, are unsubstituted. Examples of the radical R, and butyl, octyl, dodecyl, octadecenyl, eicosyl and triacontyl radicals.
The term ;'lower" used with reference to alkoxy groups herein refers to groups having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms.
The radical represented by R2 may have the same meaning as the radical Flj, but preferably represents a methyl or benzyl radical, which latter group may be substituted by one or more substituents selected from alkoxy, methyl, chloromethyl, ethyl, phenyl, chlorine and bromine groups.
The present invention further provides a process for the preparation of a compound of the invention, which comprises reacting an oxalkylated alkylamine of the general formula
in which R1, A, B,x, y and m are as defined above, with a (C1-C4)-alkylurethane, quaternizing the biscarbamate of the general formula
in which P1, A, B, x, y and m are as defined above, so obtained with an alkyl halide or an ester of alkylsulphuric or alkylphosphoric acid, or a corresponding benzyl compound to yield a compound of the general formula.
in which R1, R2, A, B, x, y and m are as defined above, subsequently reacting this compound with glyoxylic acid or a derivative thereof and, in the case where R3 represents a cation, neutralizing the reaction product with a base.
The oxalkylated alkylamines serving as starting compounds are substantially available in the form of commercial products. The polyoxyaikyl chains may be formed either from ethylene oxide alone or from propylene oxide alone (A=B). When both alkylene oxides are combined, products may be obtained which contain the ethylene oxide and propylene oxide moieties in a random distribution. Furthermore, the polyoxyalkyl chains of the oxalkylated alkylamines may be formed as block polymers.
It can be seen that in a polycarbamate of the invention the groups --(B,,-A,)),- and --(A,,- B)mmay, at each occurrence, be the same or different, preferably the same, and that for each group the radicals represented by A and B and the numbers x and y may be the same or different at each occurrence within the compound.
The oxalkylated alkylamines may be reacted with the alkylurethanes according to known processes in the presence of alkyl titanates as catalysts. The subsequent quaternization with incorporation of the R2 group may also be carried out according to known operation modes, for example with the use of dimethyl sulphate, methyl chloride, benzyl chloride or trimethyl phosphate, in a lower alcohol or toluene, and at a temperature in the range of from 60 to 700C. For continuing the reaction, glyoxylic acid, preferably in the form of glyoxylic acid hydrate, is added, the batch is heated, and the water of reaction is distilled off in water. The molar ratio of the reactants is preferably 1.5 mols of glyoxylic acid per mol of quaternized compound. As final products polymers are obtained the chain length of which is approximately defined by the value of z.In the case where R3 in the final product is a cation, the polymers obtained in the reaction with glyoxylic acid may be neutralized with the equivalent amount of a base, preferably sodium hydroxide or potassium hydroxide.
In the third step of the process of the invention, a derivative of glyoxylic acid may be used. Such derivatives are, for example, esters, salts and hydrates. As mentioned above, glyoxylic acid hydrate is preferably used. It is also possible to use, however, salts of glyoxylic acid particularly alkali metal or alkaline earth metal salts.
The present invention also provides a surfactant composition which comprises a compound of the invention with a suitable carrier.
The compounds of the invention may be used as amphoteric surfactants. Due to their good wetting and dispersing properties, they are valuable wetting agents, dyeing auxiliaries, emulsifiers, rinsing agents or softeners.
The following Examples illustrate the invention.
Example 1 72 g (0.1 mol) of the reaction product of 1 mol of stearylamine with 10 mols of ethylene oxide were reacted at 100 mm Hg and an inner temperature of 130-1 400C with 23.4 g (0.2 mol) of butylurethane and 0.7 g of isopropyl titanate as catalyst, while distilling off butanol. 13.2 g of nbutanol were obtained as distillate (89% of theory), and 80 g of biscarbamate (99% of theory) (butylurethane content 3% according to gas chromatography) were yielded.
12.5 g (0.1 mol) of benzyl chloride were added, stirring was continued for 5 hours at 1 000C, and the batch was thus quantitatively quaternized (chlorine ion content 3.7%, theory 3.8%). Subsequently, 9 g (0.1 mol) of glyoxylic acid hydrate was added, and the batch was heated further at 1 000C and a reduced pressure of 133.3 mbar, thus producing cross-linkage with distillation of 3.5 ml of water (0.195 mol). A product having an acid number of 54 (theory 57) and the following structure was obtained:
Example 2 70.8 g (0.1 mol) of oleylamine with 10 mols of ethylene oxide were reacted in an autoclave at 1 500C with 8.7 g (0.15 mol) of propylene oxide and 1 g of KOH, and the reaction product obtained was heated with stirring at 130-1 400C and 133.3 mbar with 23.4 g (0.2 mol) of butylurethane and 0.7 g of isopropyl titanate, thus distilling off 13.5 g of n-butanol (90% of theory) and obtaining 80 g (99% of theory) of biscarbamate (butylurethane content 3% according to gas chromatography).
12.6 g (0.1 mol) of dimethyl sulphate were added, stirring was continued for 3 hours at 500C, and the quaternary reaction product was quantitatively obtained (chlorine ion content 3.3%, theory 3.5%).
While adding 9 g (0.1 mol) of glyoxylic acid hydrate the batch was heated to 1 000C under a reduced pressure of 100 mm Hg, thus producing cross-linkage to give the following product:
(acid number 54, theory 57), while distilling off 3.6 ml of water (0.197 mol).
Example 3 In the autoclave, 19.9 g (0.1 mol) of isotridecylamine were gassed at 1 500C with 11.6 g (0.2 mol) of propylene oxide, 8.8 g (0.2 mol) of ethylene oxide and 1 g of KOH, and the reaction product obtained was heated with stirring to 130-1 400C under 133.3 mbar with 23.4 g (0.2 mol) of butylurethane and 0.7 g of isopropyl titanate, thus distilling off 1 3.9 g of n-butanol (93% of theory) and obtaining 48 g (98% of theory) of biscarbamate (butyiurethane content 3% according to gas chromatography).
16.1 g (0.1 mol) of 4-chlorobenzyl chloride were added, stirring was continued for 5 hours at 1 000C, and the batch was completely quaternized (chlorine ion content 5.2%, theory 5.4%).
With addition of 9 g (0.1 mol) of glyoxylic acid hydrate, the batch was heated at 1 000C under a reduced pressure of 133.3 mbar, thus distilling off 3.5 ml of water (0.195 mol), and producing crosslinkage. A product having the following structure was obtained
Claims (filed 8 Nov 1982) 1.A cross-linked polycarbamate of the general formula
in which R1, which may be the same or different at each occurrence, represents a (01-C30)-alkyl or (C1- C30)-alkenyl radical, which may be unsubstituted or substituted by one or more substituents, and R2, which may be the same or different at each occurrence, represents a benzyl radical, or a (C1- C30)-alkyl or (C1-C30)-alkenyl radical, each of which may be unsubstituted or substituted by one or more of the same substituents, with the proviso that the sum of the carbon atoms present in R1 and R2 must be at least 10, A and B, which may be the same or different at each occurrence, each represents a group of the formula -C2H40- or -C3H70-, x and y, which may be the same or different at each occurrence, is a number in the range of from zero to 30, with the proviso that the sum of x and y is at least 1, m is a number in the range of from 1 to 60, and may be the same or different at each occurrence
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (12)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    and the quaternary reaction product was quantitatively obtained (chlorine ion content 3.3%, theory 3.5%).
    While adding 9 g (0.1 mol) of glyoxylic acid hydrate the batch was heated to 1 000C under a reduced pressure of 100 mm Hg, thus producing cross-linkage to give the following product:
    (acid number 54, theory 57), while distilling off 3.6 ml of water (0.197 mol).
    Example 3 In the autoclave, 19.9 g (0.1 mol) of isotridecylamine were gassed at 1 500C with 11.6 g (0.2 mol) of propylene oxide, 8.8 g (0.2 mol) of ethylene oxide and 1 g of KOH, and the reaction product obtained was heated with stirring to 130-1 400C under 133.3 mbar with 23.4 g (0.2 mol) of butylurethane and 0.7 g of isopropyl titanate, thus distilling off 1 3.9 g of n-butanol (93% of theory) and obtaining 48 g (98% of theory) of biscarbamate (butyiurethane content 3% according to gas chromatography).
    16.1 g (0.1 mol) of 4-chlorobenzyl chloride were added, stirring was continued for 5 hours at 1 000C, and the batch was completely quaternized (chlorine ion content 5.2%, theory 5.4%).
    With addition of 9 g (0.1 mol) of glyoxylic acid hydrate, the batch was heated at 1 000C under a reduced pressure of 133.3 mbar, thus distilling off 3.5 ml of water (0.195 mol), and producing crosslinkage. A product having the following structure was obtained
    Claims (filed 8 Nov 1982) 1.A cross-linked polycarbamate of the general formula
    in which R1, which may be the same or different at each occurrence, represents a (01-C30)-alkyl or (C1- C30)-alkenyl radical, which may be unsubstituted or substituted by one or more substituents, and R2, which may be the same or different at each occurrence, represents a benzyl radical, or a (C1- C30)-alkyl or (C1-C30)-alkenyl radical, each of which may be unsubstituted or substituted by one or more of the same substituents, with the proviso that the sum of the carbon atoms present in R1 and R2 must be at least 10, A and B, which may be the same or different at each occurrence, each represents a group of the formula -C2H40- or -C3H70-, x and y, which may be the same or different at each occurrence, is a number in the range of from zero to 30, with the proviso that the sum of x and y is at least 1, m is a number in the range of from 1 to 60, and may be the same or different at each occurrence
    z is a number in the range of from 1 to 6, R3 represents a hydrogen atom or an alkali metal or alkaline earth metal cation, and Ane is a halide, alkylsulphate or alkylphosphate ion.
  2. 2. A compound as claimed in claim 1, wherein R2 represents a methyl radical
  3. 3. A compound as claimed in claim 1, which is described in anyone of Examples 1 to 3 herein.
  4. 4. A process for the preparation of a compound as claimed in claim 1, which comprises reacting an oxalkylated alkylamine of the general formula
    in which R1, A, B, x, y and m are as defined in claim 1, with a (C1-C4)-alkylurethane, quaternizing the biscarbamate of the general formula
    in which R1, A, B, x, y and m are as defined in claim 1, so obtained with an alkyl halide or an ester of alkylsulphuric or alkylphosphoric acid, or a corresponding benzyl compound to yield a compound of the general formula
    in which R1, R2, A, B, x, y and m are as defined in claim 1, subsequently reacting this compound with glyoxylic acid or a derivative thereof, and, if desired, where R3 represents a cation neutralizing the reaction product with a base or converting the cation to another cation represented by R3, or where R3 represents a hydrogen atom replacing that hydrogen atom with an alkali metal or alkaline earth metal cation.
  5. 5. A process as claimed in claim 4, wherein 1.5 mols of glyoxylic acid or derivative is used per mol of compound of the general formula (IV).
  6. 6. A process as claimed in claim 4 or claim 5, wherein glyoxylic acid is used in the form of glyoxylic acid hydrate.
  7. 7. A process as claimed in claim 4, which is carried out substantially as described in any one of Examples 1 to 3 herein.
  8. 8. A compound as claimed in claim 1, whenever prepared by a process as claimed in any one of claims 4 to 7.
  9. 9. A surfactant composition which comprises a compound as claimed in any one of claims 1 to 3 and 8 with a suitable carrier.
  10. 10. The use of a compound as claimed in any one of claims 1 to 3 and 8 or a composition as claimed in claim 9 as a wetting agent, emulsifier, dyeing auxiliary, rinsing agent or softener.
  11. 11. A method of wetting, emulsifying, dyeing, rinsing or softening an article which comprises using a compound as claimed in any one of claims 1 to 3 and 8 or a composition as claimed in claim 9.
  12. 12. A method of treating a fibre or an article which comprises applying thereto a compound as claimed in any one of claims 1 to 3 and 8, or a composition as claimed in claim 9.
GB08226259A 1981-09-16 1982-09-15 Polycarbamates and use as surfactants Withdrawn GB2108115A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19813136685 DE3136685A1 (en) 1981-09-16 1981-09-16 "POLYCARBAMATE, METHOD FOR THE PRODUCTION AND USE THEREOF"

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GB2108115A true GB2108115A (en) 1983-05-11

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GB08226259A Withdrawn GB2108115A (en) 1981-09-16 1982-09-15 Polycarbamates and use as surfactants

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010127408A1 (en) * 2009-05-07 2010-11-11 Huntsman Corporation Australia Pty. Limited Dispersants in high-electrolyte solutions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010127408A1 (en) * 2009-05-07 2010-11-11 Huntsman Corporation Australia Pty. Limited Dispersants in high-electrolyte solutions
CN102421285A (en) * 2009-05-07 2012-04-18 胡茨曼澳大利亚股份有限公司 Dispersants in high-electrolyte solutions
AU2010244980B2 (en) * 2009-05-07 2014-10-16 Indorama Ventures Oxides Australia Pty Limited Dispersants in high-electrolyte solutions
CN102421285B (en) * 2009-05-07 2015-04-01 胡茨曼澳大利亚股份有限公司 Dispersants in high-electrolyte solutions
US9265249B2 (en) 2009-05-07 2016-02-23 Huntsman Corporation Australia Pty Limited Dispersants in high-electrolyte solutions

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DE3136685A1 (en) 1983-03-24
NO823133L (en) 1983-03-17

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